WO2014070742A1 - Récupération de substances à partir d'un résidu de liqueur mère obtenu lors de la synthèse du bisphénol a - Google Patents

Récupération de substances à partir d'un résidu de liqueur mère obtenu lors de la synthèse du bisphénol a Download PDF

Info

Publication number
WO2014070742A1
WO2014070742A1 PCT/US2013/067270 US2013067270W WO2014070742A1 WO 2014070742 A1 WO2014070742 A1 WO 2014070742A1 US 2013067270 W US2013067270 W US 2013067270W WO 2014070742 A1 WO2014070742 A1 WO 2014070742A1
Authority
WO
WIPO (PCT)
Prior art keywords
mother liquor
bisphenol
phenol
liquor residue
product mixture
Prior art date
Application number
PCT/US2013/067270
Other languages
English (en)
Inventor
Ahmed YOUSSEF
Mohan KHADILKAR
Martin Oyevaar
Original Assignee
Sabic Innovative Plastics Ip B.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sabic Innovative Plastics Ip B.V. filed Critical Sabic Innovative Plastics Ip B.V.
Priority to CN201380056507.2A priority Critical patent/CN104870415A/zh
Priority to EP13792124.3A priority patent/EP2912003A1/fr
Priority to KR1020157009251A priority patent/KR20150073972A/ko
Publication of WO2014070742A1 publication Critical patent/WO2014070742A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
    • C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
    • C07C37/74—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
    • C07C37/52—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by splitting polyaromatic compounds, e.g. polyphenolalkanes

Definitions

  • Bisphenol A (2,2-bis(4-hydroxyphenyl)propane) is commercially prepared by condensing 2 moles of phenol with a mole of acetone in the presence of an acid catalyst. The phenol is present in a molar excess of the stoichiometric requirement.
  • the purification of bisphenol A is a costly multi-step procedure entailing distillations, crystallizations, solvent extractions, evaporations and like procedures.
  • a mother liquor is obtained.
  • the mother liquor after distillation, forms a mother liquor residue which contains lower boiling reaction by-products, bisphenol A and higher boiling reaction by-products to name a few components.
  • This mother liquor residue is a tarry residue which still contains valuable, recoverable materials.
  • Figure 1 is a schematic representation of an embodiment described herein.
  • bisphenol A is made by the condensation of 2 moles of a phenol with 1 mole of acetone in the presence of an acid catalyst. Phenol is used in excess of the stoichiometric requirements. Exemplary processes are described in U.S. Patents
  • reaction zone effluent is continuously withdrawn and cooled to precipitate crystalline 1:1 adduct of bisphenol A and phenol.
  • the solid adduct is filtered out, leaving a mother liquor.
  • the mother liquor comprises bisphenol A, phenol and by-products.
  • the mother liquor is treated to recover useful components such as phenol and bisphenol A.
  • the mother liquor can be heated, typically to a temperature of 55°C to 95°C, to promote isomerization of related isomers of bisphenol A to bisphenol A (2,2-bis(4-hydroxyphenyl)propane) prior to distillation.
  • the mother liquor may, alternatively or additionally, be treated with ion-exchange resins and/or filtered.
  • the mother liquor is distilled to remove bisphenol A, phenol, solvents, and other useful materials. After distillation, the remaining tarry residue is the mother liquor residue.
  • Exemplary distillation techniques include progressively (sequentially) higher vacuum/temperature conditions in order to separate the mother liquor into four fractions.
  • a first distillation column is operated under vacuum and temperature conditions to remove an overhead fraction containing relatively pure phenol (e.g. >97 purity).
  • the bottoms of the first column are fed to a second distillation column.
  • This second column operates under reduced pressures and elevated temperature conditions which remove a colored "light" fraction consisting mainly of residual isomers of bisphenol-A and Chroman along with other byproducts with known and unknown chemical structure. This lights fraction can be purged and discarded, or subjected to additional recovery by this or other processes.
  • the bottoms of the second column are fed to a third column.
  • the overheads of this third column typically contain 60-90% pure bisphenol-A depending on the temperature and pressure conditions used.
  • the bottoms of the third column contain "heavies" or tars which is the mother liquor residue used in the recovery method described herein.
  • Aromatic sulfonic acids may be represented by the general formula RC 6 H 4 SO 3 H in which R may be in any position in the phenyl ring wherein R represents hydrocarbyl having 1 to 25 carbon atoms, inclusive.
  • Exemplary aromatic sulfonic acids include p-toluenesulfonic acid and dodecylbenzene sulfonic acid
  • hydrocarbyl as used herein means the monovalent moiety obtained upon removal of a hydrogen atom from a parent hydrocarbon.
  • Representative of hydrocarbyl is alkyl of 1 to 25 carbon atoms, inclusive, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, undecyl, clecyl, dodecyl, octadecyl, nonodecyl, eicosyl, heneicysyl, docosyl, tncosyl, tetracosyl, pentacosyl and the isomeric forms thereof; aryl of 6 to 25 carbon atoms, inclusive, such as a phenyl, tolyl, xylyl, napthyl, biphenyl, tetraphenyl and the like; aralkyl of 7 to 25 carbon atoms, inclusive,
  • the aromatic sulfonic acid is present in amounts of 100 to 10,000 parts per million by weight (ppm) of mother liquor residue, more specifically, 1000 to 5000 ppm, more specifically 2100 to 2700 ppm, even more specifically 2300 to 2550 ppm.
  • Cracking occurs at temperatures of 100°C to 300°C, more specifically, 120°C to 180°C, and even more specifically 135 °C to 165 °C. Cracking can occur at a pressure of 150 to 250 millimeters (mm) Hg, more specifically, 175 to 225 mm Hg.
  • the cracker tank/heat exchanger may contain one or more internal baffles and one or more overflow baffles.
  • Mercaptans are sometimes used a co-promoters in bisphenol A synthesis. Distillation can occur in a distillation column which is located after the cracker tank/heat exchanger.
  • FIG. 1 An exemplary method is shown in Figure 1 where stream 5 is the mother liquor, 104 is a mother liquor tank, 43 and 46 are distillation steps, 33 is a condenser (also referred to as a phenol receiver) and C is where the cracking step occurs.
  • Stream 5 is a mother liquor which can comprise 75 to 85 weight percent phenol, 10 to 15 weight percent of a combination comprising bisphenol A, isomers of bisphenol A and other byproduct components.
  • Stream 1 is the mother liquor residue that can comprise 70 to 80 weight percent bisphenol A and isomers of bisphenol A, 0.5 to 3 weight percent phenol, with the balance being other byproduct components.
  • Stream 2 is a tarry mixture that can exhibit viscosities of 80 to 230 centipoise at 176 "Celsius.
  • a mother liquor comprising 80 weight percent phenol, 14.5 weight percent bisphenol A and bisphenol A isomers with the balance comprising other by-products feeds into a phenol distillation column that is equipped with Mellapak 125X in the top section and Mellapak 252Y in the bottom section as packing material.
  • a phenol distillation column that is equipped with Mellapak 125X in the top section and Mellapak 252Y in the bottom section as packing material.
  • This column may operate with an overhead pressure of 100 to 150 mm Hg.
  • the overheads stream enters a condenser and into a phenol receiver.
  • the effluent stream from the phenol receiver is mainly pure phenol (-99%).
  • a cracker is present at the bottom of the column.
  • the cracker may comprise one or more internal baffles and one or more overflow baffles and can operate at 120 to 180 °C, more specifically 135 to 165°C, and an outlet stream pressure of 150 to 250 mm Hg, more specifically 175 to 225 mm Hg. Greater than or equal to 50 weight percent of the total feed to the cracker can be converted to phenol.
  • the bottoms stream of the secondary phenol stripping column is tar to burn.
  • the secondary phenol stripping column can be a packed one comprising Koch type packing.
  • the temperature along the column's axial direction can be 120 to 180 °C.
  • Embodiment 1 A process for recovery of materials from a mother liquor residue comprising cracking a mother liquor residue with an aromatic sulfonic acid catalyst to form a cracked product mixture and separating phenol from the cracked product mixture wherein the mother liquor residue results from distillation of a mother liquor resulting from bisphenol A synthesis and isolation.
  • Embodiment 2 The process of Embodiment 1, wherein separating phenol from the cracked product mixture occurs by adding the cracked product mixture to a distillation column which precedes it in the process.
  • Embodiment 3 The process of Embodiment 1, wherein separating phenol from the cracked product mixture occurs in a distillation column which follows it in the process.
  • Embodiment 4 The process of any of Embodiments 1 to 3, wherein the aromatic sulfonic acid catalyst comprises p-toluenesulfonic acid or dodecylbenzene sulfonic acid.
  • Embodiment 5 The process of any of Embodiments 1 to 4, wherein the aromatic sulfonic acid catalyst is present in an amount of 100 to 10,000 parts per million by weight (ppm) of mother liquor residue.
  • Embodiment 6 The process of any of Embodiments 1 to 5, wherein cracking occurs at a temperature of 100°C to 300°C.
  • Embodiment 7 The process of any of Embodiments 1 to 6, wherein cracking occurs at a pressure of 150 to 250 millimeters (mm) Hg.
  • Embodiment 8 The process of any of Embodiments 1 to 7, wherein the mother liquor residue comprises 70 to 80 weight percent bisphenol A and isomers of bisphenol A and 0.5 to 3 weight percent phenol.
  • the flask was heated and once the desired temperature was reached (93 to 177°C) 2500 ppm of dodecylbenzene sulfonic acid was added using a syringe. After 30 minutes, the sample remaining in the flask was weighed (to determine mass balance), and the residue and the product collected in the second flask was analyzed by ICP. 54 weight percent of the crackable material present in the mother liquor residue (the bisphenol A and bisphenol A isomers) was converted to phenol.
  • the invention may alternately comprise, consist of, or consist essentially of, any appropriate components herein disclosed.
  • the invention may additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any components, materials, ingredients, adjuvants or species used in the prior art compositions or that are otherwise not necessary to the achievement of the function and/or objectives of the present invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de récupération de substances à partir d'un résidu de liqueur mère, le procédé comprenant le craquage d'un résidu de liqueur mère avec un catalyseur de type acide sulfonique aromatique pour former un mélange de produits craqués et la séparation du phénol contenu dans le mélange de produits craqués, le résidu de liqueur mère résultant de la distillation d'une liqueur mère obtenue lors de la synthèse et de l'isolement du bisphénol A.
PCT/US2013/067270 2012-10-29 2013-10-29 Récupération de substances à partir d'un résidu de liqueur mère obtenu lors de la synthèse du bisphénol a WO2014070742A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201380056507.2A CN104870415A (zh) 2012-10-29 2013-10-29 从双酚a合成期间获得的母液残余物中回收物质
EP13792124.3A EP2912003A1 (fr) 2012-10-29 2013-10-29 Récupération de substances à partir d'un résidu de liqueur mère obtenu lors de la synthèse du bisphénol a
KR1020157009251A KR20150073972A (ko) 2012-10-29 2013-10-29 비스페놀 a 합성시 얻어진 모액 잔류물로부터의 물질의 회수

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201261719549P 2012-10-29 2012-10-29
US61/719,549 2012-10-29

Publications (1)

Publication Number Publication Date
WO2014070742A1 true WO2014070742A1 (fr) 2014-05-08

Family

ID=49585578

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2013/067270 WO2014070742A1 (fr) 2012-10-29 2013-10-29 Récupération de substances à partir d'un résidu de liqueur mère obtenu lors de la synthèse du bisphénol a

Country Status (5)

Country Link
US (1) US9732022B2 (fr)
EP (1) EP2912003A1 (fr)
KR (1) KR20150073972A (fr)
CN (1) CN104870415A (fr)
WO (1) WO2014070742A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020114927A1 (fr) * 2018-12-07 2020-06-11 Covestro Deutschland Ag Procédé de production d'un composé hydroxy par décarboxylation en l'absence d'un catalyseur
WO2022118213A1 (fr) * 2020-12-01 2022-06-09 Sabic Global Technologies B.V. Configuration de procédé pour un seul train de purification de phénol pour la production de phénol et de bisphénol-a dans un procédé intégré

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017044229A1 (fr) 2015-09-11 2017-03-16 Sabic Global Technologies B.V. Procédé de récupération de phénol à partir d'une installation de production de bpa et installation de récupération de celui-ci
EP3383833B1 (fr) 2015-12-03 2020-11-11 SABIC Global Technologies B.V. Procédé de récupération de phénol d'une installation de production de bpa et installation pour récupérer ledit phénol
EP3615209A1 (fr) 2017-04-24 2020-03-04 Badger Licensing LLC Système catalyseur et processus de production du bisphénol-a
JP7155419B2 (ja) 2018-07-06 2022-10-18 バジャー・ライセンシング・エルエルシー ビスフェノールの製造からの残渣流の処理
KR102441561B1 (ko) 2018-12-20 2022-09-06 주식회사 엘지화학 페놀계 부산물의 분해 방법 및 이의 분해 장치

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3466337A (en) * 1967-01-30 1969-09-09 Dow Chemical Co Regeneration of phenol from bisphenol a and byproducts
US4766254A (en) 1987-10-05 1988-08-23 General Electric Company Method for maximizing yield and purity of bisphenol A
US4847433A (en) 1988-05-23 1989-07-11 General Electric Company Process for preparing bisphenol-A
EP0812815A2 (fr) * 1996-06-13 1997-12-17 General Electric Company Procédé pour la préparation de bisphénol
US6133486A (en) 1998-12-30 2000-10-17 General Electric Company Phenol recovery from BPA process waste streams

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4327229A (en) 1981-01-19 1982-04-27 General Electric Company Recovery of bisphenol-A values
DE19720540A1 (de) * 1997-05-16 1998-11-19 Bayer Ag Verfahren zur Aufarbeitung von Mutterlaugen aus der Bisphenolsynthese
US8039679B2 (en) * 2005-10-07 2011-10-18 Badger Licensing Llc Bisphenol-A plant yield enhancement

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3466337A (en) * 1967-01-30 1969-09-09 Dow Chemical Co Regeneration of phenol from bisphenol a and byproducts
US4766254A (en) 1987-10-05 1988-08-23 General Electric Company Method for maximizing yield and purity of bisphenol A
US4847433A (en) 1988-05-23 1989-07-11 General Electric Company Process for preparing bisphenol-A
EP0812815A2 (fr) * 1996-06-13 1997-12-17 General Electric Company Procédé pour la préparation de bisphénol
US6133486A (en) 1998-12-30 2000-10-17 General Electric Company Phenol recovery from BPA process waste streams

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020114927A1 (fr) * 2018-12-07 2020-06-11 Covestro Deutschland Ag Procédé de production d'un composé hydroxy par décarboxylation en l'absence d'un catalyseur
US11420918B2 (en) 2018-12-07 2022-08-23 Covestro Intellectual Property Gmbh & Co. Kg Method for producing a hydroxy compound by decarboxylation in the absence of a catalyst
WO2022118213A1 (fr) * 2020-12-01 2022-06-09 Sabic Global Technologies B.V. Configuration de procédé pour un seul train de purification de phénol pour la production de phénol et de bisphénol-a dans un procédé intégré

Also Published As

Publication number Publication date
US20140121417A1 (en) 2014-05-01
CN104870415A (zh) 2015-08-26
US9732022B2 (en) 2017-08-15
EP2912003A1 (fr) 2015-09-02
KR20150073972A (ko) 2015-07-01

Similar Documents

Publication Publication Date Title
US9732022B2 (en) Recovery of materials from a mother liquor residue
TWI306093B (en) Preparation of highly pure methyl tert-butyl ether
TWI482751B (zh) 從ｂｐａ廢棄物流中回收酚的方法
US10913699B2 (en) Method of recovering phenol from a BPA production plant and the plant for recovering the same
KR102472222B1 (ko) 아세톤을 회수하는 방법 및 이를 회수하기 위한 플랜트
US2642453A (en) Preparation of borates of tertiary alcohols
US9593090B2 (en) Alkylene oxide separation systems, methods, and apparatuses
US6133486A (en) Phenol recovery from BPA process waste streams
EP2637998B1 (fr) Procédé pour le raffinage d'un mélange d'acétyles bruts
US2874096A (en) Purification of amyl alcohol
RU2812722C1 (ru) Способ получения высокочистых октаметилциклотетрасилоксана и декаметилциклопентасилоксана разделением смеси паров метилциклосилоксанов
RU2176633C1 (ru) Способ выделения пара-трет-бутилфенола из реакционной смеси и устройство для его осуществления
KR20010073114A (ko) 용융 결정화 방법에 의한 알킬화 페놀의 정제방법
PL103405B1 (pl) Sposob otrzymywania p,p'-dwuhydroksydwufenylopropanu
EP3013793A1 (fr) Procédé amélioré pour le raffinage de nitriles
CZ280414B6 (cs) Způsob přípravy pyrokatecholového koncentrátu z fenolových směsí

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13792124

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20157009251

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2013792124

Country of ref document: EP